WO2018021211A1 - 白色ポリエステル系フィルム、積層体及び包装袋 - Google Patents

白色ポリエステル系フィルム、積層体及び包装袋 Download PDF

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Publication number
WO2018021211A1
WO2018021211A1 PCT/JP2017/026608 JP2017026608W WO2018021211A1 WO 2018021211 A1 WO2018021211 A1 WO 2018021211A1 JP 2017026608 W JP2017026608 W JP 2017026608W WO 2018021211 A1 WO2018021211 A1 WO 2018021211A1
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Prior art keywords
film
layer
polyester
heat
polyester film
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Application number
PCT/JP2017/026608
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English (en)
French (fr)
Japanese (ja)
Inventor
慎太郎 石丸
雅幸 春田
Original Assignee
東洋紡株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to MX2019000994A priority Critical patent/MX2019000994A/es
Priority to US16/320,475 priority patent/US11298927B2/en
Priority to KR1020197001313A priority patent/KR102291804B1/ko
Priority to JP2017541136A priority patent/JP6635119B2/ja
Publication of WO2018021211A1 publication Critical patent/WO2018021211A1/ja

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/30—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants by excluding light or other outside radiation
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    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Definitions

  • the present invention relates to a white polyester film excellent in heat seal strength, a laminate using the same, and a packaging bag.
  • a sealant film has been used as a packaging material for many distribution articles represented by foods, pharmaceuticals, and industrial products.
  • the innermost layer of the packaging material constituting the packaging bag, the lid material, and the like is provided with a sealant layer made of a polyolefin resin such as polyethylene or polypropylene showing high sealing strength, or a copolymer resin such as ionomer or EMMA. It is known that these resins can achieve high adhesion strength by heat sealing.
  • an unstretched sealant film made of a polyolefin-based resin as described in Patent Document 1 easily adsorbs components made of organic compounds such as fats and fragrances, so that the sealant film is in contact with the innermost layer, that is, the contents.
  • the packaging material used as a layer has the disadvantage that it is easy to change the scent and taste of the contents.
  • a sealant layer made of polyolefin resin as the innermost layer of packaging bags for chemical products, pharmaceuticals, foods, etc., it is not suitable for use because it requires measures such as adding more active ingredients in the contents in advance. There are many cases.
  • Patent Document 3 discloses a polyester-based film for sealants having non-adsorptive properties of organic compounds.
  • a high-temperature environment such as a midsummer car interior (about 80 ° C.)
  • the original shape cannot be maintained due to shrinkage of the sealant. there were.
  • Patent Documents 1 to 3 are transparent, there are many cases that are not suitable for packaging articles whose contents are altered by ultraviolet rays.
  • the polyester films as in Patent Documents 1 to 3 have a high specific gravity of 1.4, which causes a problem of high cost per weight.
  • a white polyester film which has a heat seal layer it is indicated by patent documents 4, for example.
  • the heat seal strength described in the example of Patent Document 4 is 1.4 N / 15 mm. However, this heat seal strength cannot satisfy the current required level and cannot be practically used.
  • the present invention aims to solve the problems of the prior art as described above. That is, the gist of the present invention is to provide a white polyester film suitable not only for high heat seal strength but also difficult to adsorb various organic compounds and less shrinkage during heating. The present invention is also intended to provide a laminate comprising at least one white polyester film suitable for the sealant application, and a packaging bag using the laminate.
  • the present invention has the following configuration.
  • a white polyester film comprising a polyester resin mainly composed of ethylene terephthalate and satisfying the following requirements (1) to (6).
  • At least the film has two or more layers, has at least one white layer and a heat seal layer, and at least one surface layer of the film surface is the heat seal layer.
  • the peel strength after heat sealing the heat seal layers of the polyester film at 160 ° C., 0.2 MPa for 2 seconds is 4 N / 15 mm or more and 25 N / 15 mm or less.
  • the reversible heat capacity difference before and after the glass transition temperature of the heat-seal layer of the polyester film measured from the temperature modulation DSC is 0.18 J / g ⁇ K or more and 0.35 J / g ⁇ K or less.
  • the thermal shrinkage rate when treated in hot water at 80 ° C. for 10 seconds is ⁇ 10% or more and 10% or less in both the longitudinal direction and the width direction.
  • the total light transmittance is 20% or more and 40% or less.
  • Apparent specific gravity is 0.90 or more and 1.30 or less. 2.
  • the polyester component constituting the polyester film contains at least one selected from the group consisting of neopentyl glycol, 1,4-cyclohexanedimethanol, isophthalic acid, and diethylene glycol.
  • the white polyester film described in 1. 3. 1,4-butanediol is contained in the polyester component constituting the polyester film. 2.
  • the thickness of the film is 5 to 200 ⁇ m. ⁇ 3.
  • a packaging bag comprising the white polyester film according to any one of the above in at least a part thereof. 6). 1 above. ⁇ 4.
  • a laminate comprising the white polyester film according to any one of the above as at least one layer. 7). 6. above.
  • the white polyester film of the present invention not only exhibits high heat seal strength, but also hardly adsorbs various organic compounds, so that articles containing oils and fragrances such as chemicals, pharmaceuticals and foods can be packaged hygienically. it can. Furthermore, since there is little shrinkage when a film is heated, there is little shrinkage also in a high temperature environment. Moreover, even if the white polyester film is processed, problems such as breakage hardly occur. Furthermore, the laminated body which contains the said white polyester-type film as at least one layer, and a packaging bag using the same can be provided.
  • the white polyester film of the present invention is composed of a polyester resin containing ethylene terephthalate as a main constituent and satisfies the following requirements (1) to (6).
  • At least the film has two or more layers, at least one white layer, and at least one surface layer of the film surface is a heat seal layer.
  • the peel strength after heat sealing the heat seal layers of the polyester film at 160 ° C., 0.2 MPa for 2 seconds is 4 N / 15 mm or more and 25 N / 15 mm or less.
  • the reversible heat capacity difference before and after the glass transition temperature of the heat-seal layer of the polyester film measured from the temperature modulation DSC is 0.18 J / g ⁇ K or more and 0.35 J / g ⁇ K or less.
  • the thermal shrinkage rate when treated in hot water at 80 ° C. for 10 seconds is ⁇ 10% or more and 10% or less in both the longitudinal direction and the width direction.
  • the total light transmittance is 20% or more and 40% or less.
  • Apparent specific gravity is 0.90 or more and 1.30 or less.
  • the white polyester film of the present invention that satisfies the above requirements is a white polyester film excellent in heat sealability and is suitable for sealant applications. Moreover, since it is difficult to adsorb various organic compounds, a sealant suitable as a packaging bag can be provided. Furthermore, since there is little shrinkage
  • the white polyester film of the present invention needs to have at least two layers, at least one white layer, and at least one heat seal layer. Yes, the heat seal layer needs to be on at least one surface layer of the film surface.
  • the white layer may be provided on either the surface layer or the inner layer (center portion) of the film, but is preferably designed to be the inner layer.
  • the white layer is preferably mixed with an inorganic or organic additive in order to develop a function of shielding light. Since these additives inhibit heat sealing, if the white layer is provided on both surface layers of the film, the required heat sealing strength cannot be obtained.
  • a preferred laminated structure is a two-layer / three-layer structure of heat seal layer / white layer / heat seal layer. It is preferable to use the two-layer / three-layer configuration because the heat seal strength of the film can be ensured and both surfaces of the film can be smoothed.
  • the thickness ratio of the heat seal layer in the whole film is determined by the reversible heat capacity difference of the heat seal layer described later, but from the viewpoint of the heat seal strength expression of the film, it is preferably 20% or more and 80% or less with respect to the total film thickness.
  • % To 75% is more preferable, and 30% to 70% is more preferable. If the heat seal layer is 20% or less of the total film thickness, it is difficult to make the heat seal strength 4 N / 15 mm or more, such being undesirable. On the other hand, when the heat seal layer is 80% or more of the total thickness of the film, the heat seal strength is improved, but the thickness ratio of the white layer is decreased, so that the concealability is lowered, which is not preferable.
  • the thickness ratio of the white layer in the entire film is determined by the amount of thermoplastic resin and inorganic particles that are incompatible with the polyester contained in the white layer, but is 20% of the total thickness of the film from the standpoint of film strength maintenance and concealment. % Or more and 80% or less are preferable, 25% or more and 75% or less are more preferable, and 30% or more and 70% or less are more preferable. When the thickness ratio of the white layer is less than 20%, the concealability of the film is reduced. If a large amount of thermoplastic resin or inorganic particles that are incompatible with the polyester that needs to be added to the white layer in order to compensate for this, it is not preferable because film formation becomes difficult.
  • the thickness of the white layer is greater than 80%, the thickness of the heat seal layer is relatively reduced, and the heat seal strength is lowered, which is not preferable.
  • the film can be laminated by a known method such as co-extrusion by a multi-manifold T-die or an inflation method, wet or dry lamination, or adhesion by hot melt.
  • the heat seal layer and the white layer may be non-stretched, uniaxially stretched or biaxially stretched, but are preferably stretched in at least one direction (uniaxial stretch) from the viewpoint of strength, and biaxially stretched. It is more preferable that The raw material species used for each layer and the preferred production method in the case of biaxial stretching will be described later.
  • the white polyester film of the present invention can be provided with a layer subjected to corona treatment, coating treatment or flame treatment in order to improve the adhesion of the film surface regardless of the heat seal layer or the white layer. It can be arbitrarily provided without departing from the requirements of the present invention.
  • the polyester used for the heat seal layer (hereinafter simply referred to as the heat seal layer) contained in the white polyester film of the present invention comprises an ethylene terephthalate unit as a main component. is there.
  • the polyester used for the heat seal layer preferably contains one or more monomer components (hereinafter sometimes simply referred to as amorphous components) that can be amorphous components as components other than the ethylene terephthalate unit. This is because the presence of an amorphous component makes it difficult for a reversible heat capacity difference, which will be described later, to decrease even during a film forming process such as stretching or heat setting, and heat seal strength is improved.
  • Examples of the monomer of the carboxylic acid component that can be an amorphous component include isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
  • Examples of the diol component monomer that can be an amorphous component include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, 2,2-diethyl 1,3-propanediol, and 2-n-butyl-2-ethyl.
  • amorphous carboxylic acid components and diol components it is preferable to use at least one of isophthalic acid, neopentyl glycol, 1,4-cyclohexanedimethanol, and diethylene glycol.
  • any one or more of neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol is used, and it is particularly preferable to use any one or more of neopentyl glycol and 1,4-cyclohexanedimethanol, Most preferably, neopentyl glycol is used.
  • the heat seal layer may contain components other than ethylene terephthalate and amorphous components.
  • the dicarboxylic acid component constituting the polyester include aromatic dicarboxylic acids such as orthophthalic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids.
  • aromatic dicarboxylic acids such as orthophthalic acid
  • aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid
  • alicyclic dicarboxylic acids alicyclic dicarboxylic acids.
  • trivalent or higher polyvalent carboxylic acids for example, trimellitic acid, pyromellitic acid, and anhydrides thereof
  • the components constituting the polyester include long-chain diols such as 1,4-butanediol, aliphatic diols such as hexanediol, and aromatic diols such as bisphenol A. Among these, it is preferable to contain 1,4-butanediol.
  • the preferred content of 1,4-butanediol is 4 mol% or more and 50 mol% or less, more preferably 6 mol% or more and 45 mol% or less, and particularly preferably 8 mol% or more and 40 mol or less.
  • a polyester elastomer containing ⁇ -caprolactone, tetramethylene glycol, or the like may be included as a component constituting the polyester.
  • These components not only increase the reversible heat capacity difference of the film, but also have an effect of lowering the melting point of the film, and therefore are preferable as components of the heat seal layer.
  • diols having 8 or more carbon atoms for example, octanediol
  • trihydric or higher polyhydric alcohols for example, trimethylolpropane, trimethylolethane, glycerin, diglycerin, etc.
  • various additives as required, for example, waxes, antioxidants, antistatic agents, crystal nucleating agents, thickeners, thermal stabilizers, coloring pigments, anti-coloring agents, An ultraviolet absorber or the like can be added.
  • fine particles as a lubricant that improves the slipperiness of the film to at least the surface layer of the film.
  • Any fine particles can be selected.
  • examples of inorganic fine particles include silica, alumina, titanium dioxide, calcium carbonate, kaolin, and barium sulfate.
  • organic fine particles include acrylic resin particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene. Examples thereof include particles.
  • the average particle diameter of the fine particles can be appropriately selected as necessary within a range of 0.05 to 3.0 ⁇ m as measured by a Coulter counter.
  • a method of blending the particles in the heat seal layer for example, it can be added at any stage for producing a polyester resin, but after the esterification stage or the end of the transesterification reaction, before the start of the polycondensation reaction. It is preferable to add the slurry dispersed in ethylene glycol or the like at a stage to advance the polycondensation reaction.
  • the method of blending using a machine is also included.
  • polyester raw material which comprises a white layer In the white polyester-type film of this invention, it is necessary to provide a white layer other than a heat seal layer as above-mentioned. In order to provide the white layer, a method of incorporating fine cavities therein, a method of white printing (so-called white solid printing) on the entire film surface, or the like can be employed alone or in combination. Below, the method of containing a cavity is described.
  • the polyester raw material used for the white layer it is possible to use the same polyester as the heat seal layer.
  • the polyester which consists of a suitable component for the above-mentioned heat seal layer can be used, and the polyester layer of a composition different from a heat seal layer can be provided.
  • the polyester raw material used for layers other than the heat seal layer preferably has an amorphous component amount of 25 mol% or less.
  • the amount of amorphous components in the layers other than the heat seal layer is more than 25 mol%, the mechanical strength and heat resistance of the film are lowered.
  • a method of containing the cavity for example, a foaming material or the like may be mixed and extruded, but as a preferable method, a thermoplastic resin incompatible with the polyester is mixed in the polyester constituting the white layer, A cavity is obtained by stretching in at least a uniaxial direction.
  • the thermoplastic resin incompatible with the polyester used in the white layer is arbitrary, and is not particularly limited as long as it is incompatible with the polyester.
  • polystyrene resins examples include polystyrene resins, polyolefin resins, polyacrylic resins, polycarbonate resins, polysulfone resins, and cellulose resins.
  • a polystyrene resin or a polyolefin resin such as polymethylpentene or polypropylene is preferable because of the formation of cavities.
  • Polystyrene resin refers to a thermoplastic resin containing a polystyrene structure as a basic component, and grafted or block copolymerized with other components in addition to homopolymers such as atactic polystyrene, syndiotactic polystyrene, and isotactic polystyrene.
  • Modified resins such as impact-resistant polystyrene resins and modified polyphenylene ether resins, and mixtures of thermoplastic resins having compatibility with these polystyrene resins, such as polyphenylene ether, are included.
  • the polymethylpentene resin is a polymer having units derived from 4-methylpentene-1 at 80 mol% or more, preferably 90 mol% or more, and other components include ethylene units, propylene units, butene- Examples are units derived from 1 unit, 3-methylbutene-1, and the like.
  • the polypropylene resin in the present invention includes modified resins obtained by grafting or block copolymerizing other components in addition to homopolymers such as isotactic polypropylene and syndiotactic polypropylene.
  • the thermoplastic resin incompatible with the polyester of the present invention exists in a form dispersed in various shapes such as a spherical shape, an elliptic spherical shape, or a thread shape in the polyester.
  • thermoplastic resins incompatible with the polyester constituting the white layer various additives such as waxes, antioxidants, antistatic agents, crystal nucleating agents, viscosity reducing agents, heat Stabilizers, coloring pigments, anti-coloring agents, ultraviolet absorbers and the like can be added. Further, it is preferable to add fine particles as a lubricant for improving the workability (slidability) of the film and fine particles as a concealing aid for reducing the total light transmittance.
  • fine particles any one can be selected. For example, as inorganic fine particles, silica, alumina, titanium dioxide, calcium carbonate, kaolin, barium sulfate, etc.
  • organic fine particles for example, acrylic resin Examples thereof include particles, melamine resin particles, silicone resin particles, and crosslinked polystyrene particles.
  • the average particle diameter of the fine particles is in the range of 0.05 to 3.0 ⁇ m (when measured with a Coulter counter) and can be appropriately selected as necessary.
  • the fine particles as a lubricant are preferably contained in an amount of 50 ppm or more, more preferably 100 ppm or more based on the total weight of the film. However, if the content of the lubricant is too large, the film surface unevenness may become large. Therefore, it is preferably set to 3000 ppm or less, more preferably 1000 ppm or less.
  • a method of blending the above particles into a mixture of thermoplastic resins incompatible with the polyester constituting the white layer for example, it can be added at any stage of producing the polyester resin. It is preferable to add the slurry dispersed in ethylene glycol or the like after the transesterification reaction and before the start of the polycondensation reaction to advance the polycondensation reaction. Also, a method of blending a slurry of particles dispersed in ethylene glycol or water using a vented kneading extruder and a polyester resin raw material, or a dried particle and a polyester resin raw material using a kneading extruder It is also preferable to carry out by blending method.
  • the proportion of the incompatible resin in the white layer is preferably 0% or more and 20% or less by weight. 0% indicates that no incompatible resin is contained. In this case, it is preferable that the concealability is expressed by adding fine particles as a concealing aid that reduces the total light transmittance described above. Further, if the incompatible resin is contained in an amount of 20% or more, the void content in the white layer is increased, and the physical strength of the film is lowered, which is not preferable. More preferably, it is 5% or more and 15% or less. Further, when the hiding property by a cavity developing agent (incompatible resin) such as polyolefin resin is insufficient, it is common to use inorganic particles such as titanium dioxide, calcium carbonate, barium sulfate together.
  • incompatible resin such as polyolefin resin
  • the amount of these inorganic particles is preferably 2 to 25% by weight from the viewpoint of concealability.
  • the added amount of the inorganic particles is less than 2% by weight, the concealability is insufficient, which is not preferable.
  • the added amount of inorganic particles is more than 25% by weight, the film formation becomes unstable and breakage frequently occurs, which is not preferable.
  • the polyester film of the present invention has a heat seal strength of 4 N / 15 mm or more and 25 N / 15 mm when the heat seal layers are heat sealed at a temperature of 160 ° C., a seal bar pressure of 0.2 MPa, and a seal time of 2 seconds.
  • the following is preferable.
  • the heat seal strength is preferably 5 N / 15 mm or more, and more preferably 6 N / 15 mm or more.
  • the heat seal strength is preferably large, but the upper limit obtained at present is about 25 N / 15 mm.
  • the heat-seal layer of the white polyester film of the present invention has a reversible heat capacity difference ⁇ Cp of 0.18 J, which is an index of the movable amorphous amount before and after the glass transition temperature (Tg) measured in a heat-only mode by temperature modulation DSC. / G ⁇ K to 0.35 J / g ⁇ K is preferred.
  • Tg glass transition temperature
  • an amorphous component having a weak molecular chain constraint is likely to be softened or melted by heat.
  • the higher order structure of the polymer constituting the film is divided into a crystalline phase and an amorphous phase. If the amount of the amorphous component is simply increased, the amorphous phase increases and the heat seal strength increases. It has been thought to be higher.
  • an increase in the amount of amorphous component does not increase the heat seal strength commensurate with the increased amount, particularly in a biaxially stretched film. Turned out to be prominent.
  • Non-Patent Document 1 Movable amorphous is the softest component of these three phases, and the heat capacity increases because it changes from the solid phase to the liquid phase at the Tg boundary during the temperature rising process.
  • rigid amorphous and crystals do not change from the solid phase to the melting point, the difference in heat capacity around Tg corresponds to the amount of movable amorphous.
  • the present inventors have found that a suitable heat seal strength can be ensured by controlling the movable amorphous amount of the heat seal layer within a predetermined range. If the reversible heat capacity difference ⁇ Cp is less than 0.18 J / g ⁇ K, the amount of movable amorphous necessary for the heat seal layer cannot be satisfied, and the heat seal strength falls below 4 N / 15 mm. On the other hand, the higher the reversible heat capacity difference ⁇ Cp of the heat seal layer, the better the heat seal strength and the better.
  • the upper limit of the preferred reversible heat capacity difference ⁇ Cp is 0.4 J / g ⁇ K.
  • the white polyester film of the present invention must have a thermal shrinkage rate in the width direction and in the longitudinal direction of not less than -10% and not more than 10% when treated in hot water at 80 ° C. for 10 seconds. Don't be.
  • the upper limit of hot water heat shrinkage is more preferably 9% or less, and even more preferably 8% or less.
  • the hot water heat shrinkage rate is less than zero, it means that the film is stretched, and it is not preferable because the film is difficult to maintain the original shape as in the case where the shrinkage rate is high.
  • the thickness of the white polyester-type film of this invention is not specifically limited, 3 micrometers or more and 200 micrometers or less are preferable. If the thickness of the film is less than 3 ⁇ m, the heat seal strength is insufficient and processing such as printing may become difficult, which is not preferable.
  • the film thickness may be thicker than 200 ⁇ m, but it is not preferable because the use cost of the film increases and the chemical cost increases.
  • the thickness of the film is more preferably 5 ⁇ m or more and 160 ⁇ m or less, and further preferably 7 ⁇ m or more and 120 ⁇ m or less.
  • the white polyester film of the present invention preferably has a thickness variation of 18% or less when the measurement length is 10 m in the longitudinal direction. If the thickness unevenness in the longitudinal direction is more than 18%, it is not preferable because printing defects are likely to occur when the film is printed.
  • the thickness unevenness in the longitudinal direction is more preferably 16% or less, and particularly preferably 14% or less. Moreover, although the thickness unevenness in the longitudinal direction is preferably as small as possible, this lower limit is considered to be about 1% due to the performance of the film forming apparatus.
  • Thickness unevenness in the width direction In the width direction, it is preferable that the thickness unevenness is 18% or less when the measurement length is 1 m.
  • the thickness variation in the width direction is more preferably 16% or less, and particularly preferably 14% or less.
  • the thickness variation in the width direction is preferably closer to 0%, but the lower limit is considered to be 1% from the viewpoint of the performance of the film forming apparatus and the ease of production.
  • the total light transmittance of the white polyester film of the present invention must be 20% or more and 40% or less. When the total light transmittance is 40% or more, the concealability of the film is inferior. Therefore, when used as a packaging material, ultraviolet rays hit the packaging object, and the deterioration of the packaging object is accelerated.
  • the total light transmittance of the film is preferably less than 15%, but in the present invention, 20% was the limit, so 20% was made the lower limit.
  • Apparent specific gravity The apparent specific gravity of the white polyester film of the present invention must be 0.90 or more and 1.30 or less. When the apparent specific gravity is 1.20 or less, the physical strength of the film is lowered and the film is easily broken.
  • the white layer will contain many cavities, and breakage is likely to occur during film formation. End up.
  • the apparent specific gravity is 1.30 or more, the weight per film area increases and the chemical cost increases.
  • the white polyester film of the present invention has the above 2. “Types of polyester raw materials constituting the heat seal layer” and the above 3. Used as the raw material described in “Types of polyester raw material constituting white layer”.
  • the heat seal layer is the same as described in 2. above.
  • An unstretched film obtained by melt-extrusion of the polyester raw material “type of polyester raw material constituting the heat seal layer” can be used as the sealant layer.
  • the above 1. It is preferable to laminate with a white layer stretched in at least one direction by the method described in “Layer configuration of white polyester film”. In the present invention, the above-described 2.
  • Unstretched films obtained by melting and extruding the polyester raw materials listed in “Types of polyester raw materials constituting the white layer” with separate extruders and laminating them are uniaxially stretched by a predetermined method shown below. It can also be obtained by biaxial stretching.
  • the polyester can be obtained by polycondensation by selecting the types and amounts of the dicarboxylic acid component and the diol component so as to contain an appropriate amount of a monomer that can be an amorphous component.
  • 2 or more types of chip-like polyester can be mixed and used as a raw material of a film.
  • the polyester raw material is preferably dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After the polyester raw material of each layer is dried in such a manner, it is melted at a temperature of 200 to 300 ° C. using an extruder and extruded as an unstretched film.
  • a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer.
  • the polyester raw material of each layer is dried in such a manner, it is melted at a temperature of 200 to 300 ° C. using an extruder and extruded as an unstretched film.
  • any existing method such as a T-die method or a tubular method can be employed. Thereafter, an unstretched film can be obtained by rapidly cooling the resin melted by extrusion.
  • a method of rapidly cooling the molten resin a method of obtaining a substantially unoriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly solidifying it can be suitably employed.
  • the film is preferably stretched in at least one direction of the longitudinal (longitudinal) direction or the lateral (width) direction, that is, uniaxial stretching or biaxial stretching.
  • a sequential biaxial stretching method by longitudinal stretching and transverse stretching in which longitudinal stretching is performed first and then lateral stretching will be described.
  • the main orientation direction is It doesn't matter because it only changes. Simultaneous biaxial stretching may also be used.
  • an unstretched film may be introduced into a longitudinal stretching machine in which a plurality of roll groups are continuously arranged.
  • preheating is preferably performed with a preheating roll until the film temperature reaches 65 ° C. to 90 ° C.
  • the film temperature is lower than 65 ° C., it is difficult to stretch the film in the longitudinal direction, and breakage tends to occur.
  • the temperature is higher than 90 ° C., the film tends to stick to the roll, and the roll tends to become dirty due to winding of the film around the roll or continuous production.
  • longitudinal stretching is performed.
  • the longitudinal draw ratio is preferably 1 to 5 times. Since 1 time is not longitudinally stretched, in order to obtain a lateral uniaxially stretched film, the longitudinal stretching ratio is 1 time, and in order to obtain a biaxially stretched film, the longitudinal stretching is 1.1 times or more.
  • the upper limit of the longitudinal draw ratio may be any number, but if it is too high, the transverse draw is difficult to be stretched and breakage tends to occur.
  • the shrinkage ratio in the longitudinal direction of the film caused by longitudinal stretching can be reduced.
  • the bowing phenomenon (distortion) occurring in the tenter can be reduced by relaxing in the longitudinal direction.
  • the white polyester film of the present invention uses an amorphous raw material, it is considered that shrinkage in the longitudinal direction caused by longitudinal stretching is dominant over the bowing strain. This is because only the central portion of the film shrinks in the longitudinal direction because the film is heated in a state where both ends in the film width direction are held in the subsequent lateral stretching or final heat treatment.
  • the relaxation rate in the longitudinal direction is preferably 0% or more and 70% or less (a relaxation rate of 0% indicates that relaxation is not performed).
  • the upper limit of the relaxation rate in the longitudinal direction is determined by the raw materials used and the longitudinal stretching conditions, relaxation cannot be performed beyond this.
  • the upper limit of the relaxation rate in the longitudinal direction is 70%. Relaxing in the longitudinal direction can be carried out by heating the film after longitudinal stretching at a temperature of 65 ° C. to 100 ° C. and adjusting the speed difference of the rolls.
  • the heating means any of a roll, a near infrared ray, a far infrared ray, a hot air heater and the like can be used.
  • relaxation in the longitudinal direction can be performed not only immediately after longitudinal stretching but also by, for example, lateral stretching (including a preheating zone) or final heat treatment by narrowing the clip interval in the longitudinal direction (in this case, both ends in the film width direction). Is also relaxed in the longitudinal direction, which reduces bowing distortion) and can be performed at any time.
  • the film is preferably cooled once, and is preferably cooled with a cooling roll having a surface temperature of 20 to 40 ° C.
  • transverse stretching After longitudinal stretching, it is preferable to perform transverse stretching at a stretching ratio of about 3.5 to 5 times at 65 ° C. to 110 ° C. with both ends of the film in the width direction held by clips in a tenter. Prior to the stretching in the transverse direction, preheating is preferably performed, and the preheating is preferably performed until the film surface temperature reaches 75 ° C. to 120 ° C. After transverse stretching, the film is preferably passed through an intermediate zone where no aggressive heating operation is performed. Since the temperature in the next final heat treatment zone is higher than that in the tenter transverse stretching zone, the heat (hot air itself or radiant heat) in the final heat treatment zone flows into the transverse stretching step unless an intermediate zone is provided.
  • the temperature of the transverse stretching zone is not stable, not only the thickness accuracy of the film is deteriorated, but also physical properties such as heat seal strength and shrinkage rate are varied. Therefore, it is preferable to carry out the final heat treatment after the film after transverse stretching passes through the intermediate zone and passes a predetermined time.
  • this intermediate zone when a strip-shaped paper piece is hung in a state where the film is not passed through, the accompanying flow accompanying the running of the film, the transverse stretching zone and the final It is important to block hot air from the heat treatment zone.
  • a transit time of about 1 to 5 seconds is sufficient for the intermediate zone. If it is shorter than 1 second, the length of the intermediate zone becomes insufficient, and the heat shielding effect is insufficient.
  • the intermediate zone is long, but if it is too long, the facility becomes large, so about 5 seconds is sufficient.
  • heat treatment is preferably performed in the final heat treatment zone at a temperature not lower than the transverse stretching temperature and not higher than 180 ° C. If the heat treatment temperature is not higher than the transverse stretching temperature, the effect as a heat treatment is not exhibited. In this case, the 80 ° C. hot water shrinkage of the film is higher than 15%, which is not preferable. As the heat treatment temperature increases, the shrinkage of the film decreases. However, if the temperature exceeds 180 ° C., the surface of the film becomes rough and the printability deteriorates, which is not preferable.
  • the shrinkage rate in the width direction can be reduced by reducing the distance between the clips of the tenter by an arbitrary magnification (relaxation in the width direction). Therefore, in the final heat treatment, it is preferable to perform relaxation in the width direction in a range of 0% to 10% (a relaxation rate of 0% indicates that relaxation is not performed). The higher the relaxation rate in the width direction, the lower the shrinkage rate in the width direction.
  • the upper limit of the relaxation rate is the raw material used, the stretching conditions in the width direction, and the heat treatment temperature. Because it depends on the situation, you cannot relax beyond this.
  • the upper limit of the relaxation rate in the width direction is 10%.
  • the passing time through the final heat treatment zone is preferably 2 seconds or more and 20 seconds or less.
  • the passage time is 2 seconds or less, the surface temperature of the film passes through the heat treatment zone without reaching the set temperature, so that the meaning of the heat treatment becomes meaningless.
  • the longer the passage time the higher the effect of the heat treatment, so that it is preferably 2 seconds or more, and more preferably 5 seconds or more.
  • the passage time is increased, the facility becomes enormous, so that it is sufficient in practice to be 20 seconds or less. After that, a white polyester film roll can be obtained by winding the film while cutting and removing both ends.
  • the white polyester film mentioned in the above section 5.1 “Filming by coextrusion” can be adhered to other polyester films.
  • an unstretched film is used as a heat seal layer, it is preferable to adhere to a polyester film that is stretched in at least one direction.
  • the adhering method is as described in 1. Examples include the method described in “Layer configuration of white polyester film”. In the case of dry lamination, a commercially available adhesive for dry lamination can be used.
  • Representative examples include Dick Dry (registered trademark) LX-703VL manufactured by DIC, KR-90 manufactured by DIC, Takenate (registered trademark) A-4 manufactured by Mitsui Chemicals, and Takerak (registered trademark) A-905 manufactured by Mitsui Chemicals. Etc.
  • the present invention will be specifically described using examples and comparative examples.
  • the present invention is not limited to the embodiments of the examples, and may be appropriately changed without departing from the spirit of the present invention. Is possible.
  • the evaluation method of the film is as follows. If the longitudinal direction and the width direction cannot be specified immediately because the film area is small, etc., the longitudinal direction and the width direction may be determined and measured. On the other hand, even if it is 90 degrees different, there is no particular problem.
  • the cut film sample was observed by an electron scanning microscope (SEM) for cross section to confirm whether any layers other than the heat seal layer were cut.
  • SEM electron scanning microscope
  • a notch was made in the film and it was torn by hand, and peeling between layers (notch) of the torn part was peeled off with tweezers.
  • the peeled heat seal layer sampled the part 1 cm or more away from the notch.
  • the inflection point is obtained using the attached analysis software (TA Analysis manufactured by TA Instruments), and the heat capacity difference before and after the inflection point (glass transition point) is determined according to the following formula 1.
  • Heat seal strength was measured according to JIS Z1707. A specific procedure is shown. Heat seal layers that were not subjected to sample coating or corona treatment were adhered to each other with a heat sealer. The sealing conditions were an upper bar temperature of 160 ° C., a lower bar temperature of 100 ° C., a pressure of 0.2 MPa, and a time of 2 seconds. The adhesive sample was cut out so that the seal width was 15 mm. The peel strength was measured using a universal tensile tester “DSS-100” (manufactured by Shimadzu Corporation) at a tensile speed of 200 mm / min. The peel strength is indicated by the strength per 15 mm (N / 15 mm).
  • Total light transmittance Based on JIS-K-7136, it measured using the haze meter (Nippon Denshoku Industries Co., Ltd. 300A). In addition, the measurement was performed twice and the average value was calculated
  • the shrinkage rate in the direction of further shrinkage was adopted.
  • This shrinkage rate was evaluated as follows as an appearance after being left in a high temperature environment.
  • Judgment ⁇ Judgment of shrinkage from original shape is less than 2%
  • Decrease rate from original shape is 2% or more and 5% or less
  • Judgment ⁇ Proportion of shrinkage from original shape is more than 5%
  • the film was sampled into a wide band having a length of 40 mm and a width of 1.2 m, and a measuring speed of 5 m / min. Then, the thickness was continuously measured along the width direction of the film sample (measurement length was 1 m). The maximum thickness at the time of measurement was Tmax., The minimum thickness was Tmin., The average thickness was Tave., And the thickness unevenness in the longitudinal direction of the film was calculated from Equation 4 above.
  • Adsorption amount Film weight after penetration-Film weight before penetration This amount of adsorption was determined as follows. Judgment ⁇ 0 mg or more and 5 mg or less judgment ⁇ higher than 5 mg, 10 mg or less judgment ⁇ higher than 10 mg
  • polyester (1) was obtained. This polyester (1) is polyethylene terephthalate.
  • the intrinsic viscosities of each polyester were 2: 0.78 dl / g, 3: 0.73 dl / g, 4: 0.73 dl / g, 5: 0.80 dl / g, and 6: 0.75 dl / g, respectively. It was.
  • polyester film 1 As raw materials for the heat seal layer (A layer), polyester 3, polyester 5 and polyester 6 were mixed in a mass ratio of 84: 10: 6. As a raw material for the white layer (B layer), in addition to polyester 1, polyester 3, and polyester 5, polypropylene (FS2011DG3, manufactured by Sumitomo Chemical Co., Ltd.) and titanium dioxide (TA-300, manufactured by Fuji Titanium) are each in a mass ratio of 10: 60: 10: 10. : 10 mixed.
  • FS2011DG3 polypropylene
  • TA-300 titanium dioxide
  • the mixed raw materials of the A layer and the B layer were respectively fed into separate twin screw extruders, melted at 270 ° C., joined by a feed block in the middle of the flow path, laminated in a sheet form from a T die, and discharged.
  • the discharged laminated sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a layered structure of A layer / B layer / A layer. Note that the resin discharge rate was adjusted so that the layer ratio at this time was 50/50 for the A layer / B layer.
  • the unstretched film obtained by cooling and solidification was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on a preheating roll until the film temperature reached 82 ° C., and then stretched 3.8 times.
  • the film immediately after longitudinal stretching was passed through a heating furnace set at 100 ° C. with a hot air heater, and a 20% relaxation treatment was performed in the longitudinal direction using the difference in speed between the heating furnace inlet and outlet rolls. Thereafter, the longitudinally stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C.
  • the film after the relaxation treatment was guided to a transverse stretching machine (tenter) and preheated for 5 seconds until the surface temperature reached 95 ° C., and then stretched 4.0 times in the width direction (lateral direction).
  • the film after transverse stretching was directly introduced to the intermediate zone and allowed to pass in 1.0 second.
  • hot air from the final heat treatment zone and the transverse stretching zone so that when the strip-shaped paper piece is hung in a state where the film is not passed through, the paper piece hangs almost completely in the vertical direction.
  • the hot air from was cut off. Thereafter, the film that passed through the intermediate zone was guided to the final heat treatment zone and heat treated at 130 ° C. for 5 seconds.
  • polyester 3 polyester 5 and polyester 6 were mixed at a mass ratio of 84: 10: 6.
  • polyester 3 and polyester 5 polypropylene (FS2011DG3 manufactured by Sumitomo Chemical) and titanium dioxide (TA-300 manufactured by Fuji Titanium) were mixed at a mass ratio of 10: 50: 10: 20: 10, respectively. did.
  • the mixed raw materials of the A layer and the B layer were respectively fed into separate twin screw extruders, melted at 270 ° C., joined by a feed block in the middle of the flow path, laminated in a sheet form from a T die, and discharged.
  • the discharged laminated sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a layered structure of A layer / B layer / A layer. Note that the resin discharge rate was adjusted so that the layer ratio at this time was 30/70 for the A layer / B layer. Thereafter, a film was formed under the same conditions as for the polyester film 1 to obtain a biaxially stretched film having a width of 500 mm and a thickness of 30 ⁇ m. The manufacturing conditions are shown in Table 2.
  • polyester 1, polyester 3, polyester 5, and polyester 6 were mixed at a mass ratio of 24: 60: 10: 6.
  • polyester 1, polyester 3, and polyester 5 in addition to polyester 1, polyester 3, and polyester 5, polypropylene (FS2011DG3 manufactured by Sumitomo Chemical) and titanium dioxide (TA-300 manufactured by Fuji Titanium) were mixed at a mass ratio of 10: 60: 10: 10: 10, respectively. did.
  • the mixed raw materials of the A layer and the B layer were respectively fed into separate twin screw extruders, melted at 270 ° C., joined by a feed block in the middle of the flow path, laminated in a sheet form from a T die, and discharged.
  • the discharged laminated sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a layered structure of A layer / B layer / A layer. Note that the resin discharge rate was adjusted so that the layer ratio at this time was 50/50 for the A layer / B layer.
  • the unstretched film obtained by cooling and solidification was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on a preheating roll until the film temperature reached 90 ° C., and then stretched 3.8 times. The film immediately after longitudinal stretching was passed through a heating furnace set at 110 ° C.
  • the longitudinally stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C.
  • the film after the relaxation treatment was guided to a transverse stretching machine (tenter), preheated for 5 seconds until the surface temperature reached 100 ° C., and then stretched 4.0 times in the width direction (lateral direction).
  • the film after transverse stretching was directly introduced to the intermediate zone and allowed to pass in 1.0 second.
  • the film After passing through the final heat treatment zone, the film was cooled, both edges were cut and removed, and wound into a roll with a width of 500 mm, thereby continuously producing a biaxially stretched film having a thickness of 30 ⁇ m over a predetermined length. .
  • the manufacturing conditions are shown in Table 2.
  • polyester 1, polyester 3, polyester 5 and polyester 6 are mixed at a mass ratio of 24: 60: 10: 6, and after melting in a twin screw extruder, melted at 270 ° C. Was discharged.
  • the discharged sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a single layer structure consisting of only the A layer.
  • the unstretched film was guided to a transverse stretching machine (tenter), pre-heated for 5 seconds until the surface temperature reached 80 ° C., and then stretched 4.0 times in the width direction (lateral direction). The film after transverse stretching was directly introduced to the intermediate zone and allowed to pass in 1.0 second.
  • the film After passing through the final heat treatment zone, the film was cooled, both edges were cut and removed, and wound into a roll having a width of 500 mm to continuously produce a uniaxially stretched film having a thickness of 15 ⁇ m over a predetermined length.
  • the manufacturing conditions are shown in Table 2.
  • polyester 1, polyester 2, polyester 4, polyester 5 and polyester 6 are mixed at a mass ratio of 5: 86: 2: 2: 5, and after being put into a twin screw extruder, melted at 270 ° C., The sheet was discharged from a T die. The discharged sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a single layer structure consisting of only the A layer. By cutting and removing both edges of the unstretched film obtained by cooling and solidification and winding it into a roll with a width of 500 mm, an unstretched film having a thickness of 15 ⁇ m was obtained. The manufacturing conditions are shown in Table 2.
  • the unstretched film obtained by cooling and solidifying was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on a preheating roll until the film temperature reached 95 ° C., and then stretched 3.8 times.
  • the film immediately after longitudinal stretching was passed through a heating furnace set at 110 ° C. with a hot air heater, and a 20% relaxation treatment was performed in the longitudinal direction using the difference in speed between the inlet and outlet rolls of the heating furnace. Thereafter, the longitudinally stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C.
  • the film after the relaxation treatment was guided to a transverse stretching machine (tenter), preheated for 5 seconds until the surface temperature reached 100 ° C., and then stretched 4.0 times in the width direction (lateral direction).
  • the film after transverse stretching was directly introduced to the intermediate zone and allowed to pass in 1.0 second.
  • hot air from the final heat treatment zone and the transverse stretching zone so that when the strip-shaped paper piece is hung in a state where the film is not passed through, the paper piece hangs almost completely in the vertical direction.
  • the hot air from was cut off. Thereafter, the film that passed through the intermediate zone was guided to the final heat treatment zone and heat treated at 130 ° C. for 5 seconds.
  • Polyester 1 and polyester 6 were mixed as a raw material for the A layer at a mass ratio of 94: 6, charged into a twin screw extruder, melted at 270 ° C., and discharged from a T die into a sheet.
  • the discharged sheet was cooled on a chill roll set at a surface temperature of 30 ° C. to obtain an unstretched film having a single layer structure consisting of only the A layer.
  • the unstretched film obtained by cooling and solidification was guided to a longitudinal stretching machine in which a plurality of roll groups were continuously arranged, preheated on a preheating roll until the film temperature reached 90 ° C., and then stretched 3.8 times.
  • the film immediately after longitudinal stretching was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C. without passing through a heating furnace (without relaxing treatment).
  • the film after longitudinal stretching was guided to a transverse stretching machine (tenter) and pre-heated for 5 seconds until the surface temperature reached 100 ° C., and then stretched 4.0 times in the width direction (lateral direction).
  • the film after transverse stretching was directly introduced to the intermediate zone and allowed to pass in 1.0 second. In the middle zone of the tenter, hot air from the final heat treatment zone and the transverse stretching zone so that when the strip-shaped paper piece is hung in a state where the film is not passed through, the paper piece hangs almost completely in the vertical direction. The hot air from was cut off.
  • the film that passed through the intermediate zone was guided to the final heat treatment zone and heat treated at 200 ° C. for 5 seconds.
  • 3% relaxation treatment was performed in the width direction by narrowing the clip interval in the film width direction simultaneously with the heat treatment.
  • the film was cooled, both edges were cut and removed, and a biaxially stretched film having a thickness of 15 ⁇ m was continuously produced over a predetermined length by winding it into a roll having a width of 500 mm. .
  • the manufacturing conditions are shown in Table 2.
  • Example 1 to 4 polyester films 1 to 4 were used as they were, respectively.
  • the A layer is a heat seal layer and the B layer is a white layer.
  • Example 5 to 8 an evaluation film was prepared by laminating a heat seal layer and a white layer. The two films were bonded using a dry lamination adhesive (Takelac (registered trademark) A-950 manufactured by Mitsui Chemicals). Table 3 shows combinations of laminated films and their evaluation results.
  • Comparative Examples 1 to 4 In Comparative Examples 1 to 4, a heat seal layer and a white layer were laminated in the same manner as in Examples 5 to 8.
  • a polypropylene sealant P1128-20 ⁇ m manufactured by Toyobo Co., Ltd.
  • Table 3 shows combinations of laminated films and their evaluation results.
  • the seal temperature was set to 140 ° C. because the film melted and adhered to the seal bar when the seal temperature was 160 ° C.
  • the sealing temperature when a bag was produced only in Comparative Example 4 was 140 ° C.
  • the films of Examples 1 to 6 all have a reversible heat capacity difference ⁇ Cp of the heat seal layer within a predetermined range, and the heat seal strength, shrinkage rate, light transmittance, apparent specific gravity, thickness unevenness, high temperature environment It was excellent in appearance, aroma retention, and adsorptivity after being left, and a good evaluation result was obtained.
  • the DSC measurement could be performed normally.
  • the film of Comparative Example 1 satisfies ⁇ Cp of the heat seal layer, and is excellent in heat seal strength, thickness unevenness, aroma retention, and adsorptivity, but has a high shrinkage ratio, and therefore after being left in a high temperature environment The appearance of was poor. Furthermore, the film of Comparative Example 1 was a film having a high total light transmittance and a high apparent specific gravity. Further, the film of Comparative Example 2 also satisfies ⁇ Cp of the heat seal layer, and is excellent in heat seal strength, shrinkage rate, thickness unevenness, aroma retention, and adsorptivity, but has a high total light transmittance, I did not meet the requirements.
  • the film of Comparative Example 3 had a low ⁇ Cp of the heat seal layer, the film peeled immediately even after heat sealing, and the heat seal strength was almost zero.
  • the film of Comparative Example 4 was excellent in heat seal strength, since polypropylene was used for the heat seal layer, the adsorptivity of menthol and limonene was x, and the aroma retaining property was ⁇ .
  • the white polyester film of the present invention not only exhibits high heat seal strength, but also hardly adsorbs various organic compounds, so that articles containing oils and fragrances such as chemicals, pharmaceuticals and foods can be packaged hygienically. And can be suitably used as a sealant application. Moreover, it is also possible to laminate

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Polyesters Or Polycarbonates (AREA)
PCT/JP2017/026608 2016-07-27 2017-07-24 白色ポリエステル系フィルム、積層体及び包装袋 WO2018021211A1 (ja)

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MX2019000994A MX2019000994A (es) 2016-07-27 2017-07-24 Pelicula blanca de poliester, laminado y bolsa para embalar.
US16/320,475 US11298927B2 (en) 2016-07-27 2017-07-24 White polyester film, laminate, and packaging bag
KR1020197001313A KR102291804B1 (ko) 2016-07-27 2017-07-24 백색 폴리에스테르계 필름, 적층체 및 포장봉지
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